Ductile brazing alloy containing reactive metals and precious metals

ABSTRACT

Reactive metal-precious metal ductile alloys containing controlled amounts of Cu and Ni and mixtures thereof are suitable for brazing ceramics, other non-metallic and metallic materials.

This application is a continuation of application Ser. No. 672,057,filed 11/16/84, now U.S. Pat. No. 4,604,328 which was a continuation ofSer. No. 422,625, filed 9/24/82, now abandoned.

FIELD OF INVENTION

This invention relates to brazing alloys. More particularly it relatesto brazing alloys containing a reactive metal having a liquidustemperature above about 890° C.

BACKGROUND

Alloys containing titanium are known. These alloys contain relativelyhigh levels of titanium. Generally the titanium content is above about7% by weight. These alloys are not ductile and cannot be rolled to afoil in a satisfactory manner and upon brazing contain a brittledispersed phase.

With regard to brazing a ceramic material to a metal member, thereliability of the brazed joint is good when the brazing alloy isductile. A ductile alloy is necessary because of the thermal expansionmismatch between metal and ceramic members.

SUMMARY OF THE INVENTION

Reactive metal-precious metal alloys containing specified amounts ofnickel, copper, chromium, molybdenum and mixtures thereof have liquidustemperatures in the range of from about 890° C. to about 1400° C.; areductile and after brazing are relatively free of hard dispersed phases.

DETAILS OF PREFERRED EMBODIMENTS

For a better understanding of the present invention, together with otherand further objects, advantages and capabilities thereof, reference ismade to the following disclosure and appended claims in connection withthe above description of some of the aspects of the invention.

The amount of the reactive metal in the alloys of this invention whichalso contain a precious metal selected from gold, palladium and mixturesthereof and a third metal seleted from Ni, Cu, Cr, Mo and mixturesthereof cannot appreciably exceed about 5% by weight and achieve aductile material which upon brazing is free of dispersed phases.

The amount of reactive metal in the alloys of this invention is fromabout 0.1% by weight to about 5% by weight, with from about 1% by weightto about 3% by weight being preferred. By reactive metal, within thecontext of this disclosure, is meant titanium, zirconium, vanadium andmixtures thereof. While titanium generally is the preferred reactivemetal, alloy compositions of Ti-Zr and Ti-V are equally effective.

The weight percent of the precious metal, which is selected from gold,palladium and mixtures thereof, can vary from about 25% by weight toabout 85% by weight. The preferred level is generally from about 28% byweight to about 81% by weight.

The weight precent of the third metal, which is selected from copper,nickel and mixtures, thereof can vary from about 15% by weight to about70% by weight. When nickel is the third metal it is preferably presentin amounts of from about 3% by weight to about 40% by weight. Whencopper is the third metal it is preferably present in amounts of fromabout 20% by weight to about 80% by weight.

Chromium is an optional metal which can be added to the alloys of thisinvention to improve corrosion and oxidation resistance. For thispurpose, chromium is added in an amount from about 2% by weight to about30% by weight and preferably from about 5% to about 10% by weight.

Molybdenum is an optional metal which can be added to the alloys of thisinvention to prevent high temperature creep. The metal can be added fromabout 6 to 40% by weight.

Various alloys are prepared by skull melting using a tungsten electrodeand an argon atmosphere. The alloys are ductile and are rolled to foilsusing, an intermediate vacuum anneal. The thickness of the foil is offrom about 2 to 6 mils.

The compositions of the alloys and their flow temperatures are given inTable 1.

                  TABLE I                                                         ______________________________________                                        Element (% by weight)  Brazing                                                Alloy  Ti    Au    Pd  Cu   Ni  Cr  Mo   Temperature °C.               ______________________________________                                        1      2     68     8       22           1075                                 2      2     48    25       25           1175                                 3      2     28    34       36           1200                                 4      2     35        63                1050                                 5      1     81             18           1010                                 6      3           58       39           1280                                 7      2     70             22   6       1030                                 8      2     35        60    3           1070                                 9      3           52       35  10       1290                                 10     2     81        17                 990                                 11     2           52       29  11   6   1320                                 12     2                    69      29   1440                                 13     2           40  58                1190                                 ______________________________________                                    

The alloys are suitable for a variety of brazing applications. Forexample, alloys 4, 8 and 10 are useful for brazing ceramics to ferrousbase alloys such as brazing alumina to an iron-nickel-cobalt alloy knownas Kovar, a trademark of Westinghouse Electric Corporation. Alloys 1, 2,3 and 5 are useful for brazing superalloys such as thenickel-iron-chromium alloy Inconel, a trademark of International NickelCo. Alloy 7 is useful for brazing stainless steels such as 304 stainlesssteel.

EXAMPLE 1

Alloys 1, 2 and 3 without Ti are currently produced by WESGO Division ofGTE Products Corporation and sold under the trademarks Palniro 7,Palniro 1, and Palniro 4, respectively. These alloys which all are usedto braze superalloys in aircraft combine components show excellentbrazing characteristics and oxidation and fatigue resistance. When thesealloys are used to braze superalloys such as the nickel base alloyHastelloy X, a trademark of Cabot Corp., Inconel 718 and othersuperalloys containing Al and/or Ti, nickel plating of these superalloysprior to brazing is required to insure proper wetting. Use of alloys 1,2 or 3 without prior nickel plating of Inconel 718 produce excellentbrazes to 410 stainless steel in a vacuum of 10⁻⁵ mm Hg at respectivebraze alloy flow temperature listed in Table 1.

EXAMPLE 2

A 2 mil foil of alloy 4 was placed between a 97.5% alumina body producedand sold by WESGO Division of GTE Products Corporation under thetrademark of Al--300, and a Kovar metallic sheet and brazed under 10³¹ 5mm Hg at 1050° C. The alloy melted and brazed the alumina body to themetal sheet with excellent results. Another Kovar sheet was placed onthe opposite face of the same alumina body with a 2 mil foil of alloy 10placed therebetween. The total assembly was heated to 980° C. in a 10⁻⁵mm Hg vacuum resulting in a second successful braze on a same assemblywithout melting the original braze. The technique is called stepbrazing; additional brazes can be carried out using lower temperaturebrazing alloys on the new assembly.

EXAMPLE 3

Alloy 8 without titanium is produced and sold under a trademark ofNicoro by WESGO Division of GTE Products Corporation. An alloy 8 foilhaving a 2 mil thickness was placed between Al--300 alumina ceramic anda Kovar alloy sheet and was heated to 1070° C. in 10⁻⁵ mm Hg vacuumresulting in an excellent brazed joint.

EXAMPLE 4

An alloy consisting of, in percent by weight, 82 gold and 18 nickelproduced and sold under the trademark Nioro by WESGO Division of GTEProducts Corporation is used to braze aircraft turbine componentsbecause of its excellent fatigue property and brazing capability. Inorder to braze Hastelloy X using Nioro alloy, the Hastelloy X surfacemust first be nickel plated to about 1 mil thickness. In using alloys 5and 7 to braze Hastelloy X (without nickel plating) to 410 stainlesssteel, 4 mil foils of alloys 5 and 7 were placed between two assemblies,respectively, of Hastelloy X and 410 stainless steel. These twoassemblies were placed in vacuum furnace and heated to 1030° C. in a10⁻⁵ mm Hg vacuum. Excellent brazes were made by both alloys; exposingthe assemblies to air at 900° C. produced greater discoloration in thechromium-free alloy (alloy 5) indicating, however, that for severeenvironments, chromium in the alloy is preferred.

EXAMPLE 5

Alloy 6 is useful for brazing metal to metal, ceramic to ceramic, andceramic to metal for high temperature applications. Alloy 9 with 10%chromium has the same capability with the additional characteristic ofhigh temperature oxidation resistance. To test the ceramic to ceramicbonding capability, three ceramic flocks, each being 1"×1"×1/2" and madeof Al--300 alumina ceramic, were stacked with a 2 mil alloy 6 foilbetween blocks 1 and 2, and a 2 mil alloy 9 foil between blocks 2 and 3.This asssembly was placed in a vacuum furnace and heated to 1290° C.under 10⁻⁵ mm Hg vacuum and cooled. The polished cross section showedexcellent bonding by both alloys 6 and 9. An oxidation test at 900° C.in air showed slightly greater oxidation discoloration on thechromium-free alloy 6.

EXAMPLE 6

Two graphite blocks having dimensions of 1"×1"×1/2" were bonded acrossthe 1"×1" face using a 2 mil piece of alloy 12 at 1440° C. under 10⁻⁵ mmHg vacuum. The resulting brazed joint was excellent.

EXAMPLE 7

A 4 mil foil of alloy 13 was used to edge bond a 410 stainless steelpiece measuring 1"×1/2"×30 mil to a 1"×1"×.100" alumina substrate at10³¹ 5 mm Hg under a 1190° C. brazing temperature. The brazed joint wasstrong and had a good fillet.

EXAMPLE 8

A 4 mil foil of alloy 11 was placed between two Al--300 alumina ceramic1"×1"×.25" blocks. The assembly was heated to 1320° C. in 10⁻⁵ mm Hgvacuum and cooled. Examination of the polished section of the brazedmaterial showed an excellent metal to ceramic bond.

While there has been shown and described what are at present consideredthe preferred embodiments of the invention, it will be obvious to thoseskilled in the art that various changes and modifications may be madetherein without departing from the scope of the invention as defined bythe appended claims.

What is claimed is:
 1. A brazing alloy consisting essentially of fromabout 0.25% to about 5% by weight of a reactive metal selected from thegroup consisting of titanium, vanadium, zirconium and mixtures thereof,from about 25% by weight to about 85% by weight of a gold-palladiummixture and from about 15% by weight to about 70% by weight of a thirdmetal selected from the group consisting of copper, nickel and mixturesthereof.
 2. An alloy according to claim 1 wherein said reactive metal istitanium.
 3. An alloy according to claim 2 wherein said third metal iscopper in an amount of from about 5% to about 65% by weight.
 4. An alloyaccording to claim 2 wherein said third metal is nickel in amounts offrom about 17% by weight to about 40% by weight.